Water-soluble azo dyes from



Reissued Mar. 9 1943 U NIT ED STATES PAT E N T OF F l C E WATER-SOLUBLEAZO DYES FROM AMINO- ARYLOXY-ACYL-DIAMINES ChilesE. Sparks, Wilmington, and James W. Libby, In, 'Claymont, Del., assig'nors to E. I. du Pont -de Nemours & Company, Wilmington,

'D'eL, a corporationcf Delaware No Drawing.

Original No. 2,266,823, dated December '23, 1941, Serial No. 345,171, July 12, 1940. Applicationfor reissue July 7, 1942, Serial 1'7 Claims. (Cl. 260-145) of the invention will be apparent from the following description.

The objects of the invention are attained in general by providing the type of tetrakisazo compound hereinafter to be described, making direct dyeings and thereafter appropriately treating the direct dyeings with formaldehyde to form a formaldehyde complex on the fiber.

The new compounds are represented in general which are recorded in the literature, are very use- .10 by the formula RIIIII ful because they are substantive to cellulose and possess bright shades which are moderately fast to light. These products are very fugitive to washing. The dyeings show considerable loss in strength when washed and they impart-an .undesirable stain'in washing to associated uncolored or differently colored fibers. It is therefore :desirable to provide direct colors which possess good washing fastness and do not stain :other associated fibers.

Heretofore poor washing fastness has beenimproved in the so-called 'diazo colors by providing substantive diazotizable colors, diazotizing ---the direct colors on the fiber and then developing with suitable coupling components. These cliazo colors are faster to washing but duller in shade than the corresponding direct colors. Among the objections to developed diazo colors are the considerable shade change which usually results on development'and the relatively .high expense "for materials and processing to be borne by the dyer who must carry out the development.

It is among the objects of this invention to provide 'azo dyes which'combine the advantages of simplicity of application and ireedomrfrom shade change upon dyeing of the direct colors with the washing fastness of the diazo colors. Another object of the invention is to provide direct dyeings which are capable of beingafter-treated .by simple procedures. Another object of the invention is to provide dyes which will show'little if any shade change bysuch after-treatment. .Another object is to provide dyeings having Washing 'iastness equal to or surpassing that of diazo colors. Another object of the inventionis to-provide methods of applying the colors and of increasing their light iastness. Still other objects in which Q is the radical of a straighter branched chain aliphatic hydrocarbon compound having 1 to 6 carbons; R""' is one of a group consisting 01 hydrogen, alkyl having 1 to 6 carbons, the

corresponding alkoxy groups, hydroxy, sulfonic acid and carboxy; R is from the group consisting of hydrogen, alkyl having 1 to 6 carbons, the corresponding alkoxy groups, halogen, carboxy, and sulfonic acid; n is 1 to 2; HN--ArylNI-Iz is a radical from the benzene and naphthalene series represented by the formulae set- 15 and The Y compounds of theabove general formula are amine substituted coupling components of the benzene and naphthalene series represented by the following formulae can be present.

These compounds can be made in general by tetrazotizing the described amino-aryloxy-acyldiamine and coupling with two molecular equivalents of the compound Y, thus forming a disazo compound having two primary arylamine groups. The disazo compound is tetrazotized and coupled with two molecular equivalents of a compound of the described dihydroxy benzene series. In the form of any of their alkali metal salts, the compounds are soluble in water and dyeings can be made from such solutions. For exceptionally good washing fastness, the dyeings are treated with formaldehyde in a suitable manner. If desired, the direct or the formaldehyde treated dyeings can be treated with metal salt solutions which gives deeper shades with improvement in light fastness.

These compounds are valuable as direct dyes for cellulosic materials, such as cotton, regenerated cellulose rayon and similar dyeable substances. They produce dyeings in bright shades.

, Superior washing fastness without loss of brightness or marked change of shade is attained by i f: after-treating the dyeings with formaldehyde,

Example I A slurry containing 12.9 parts of 3-(4'-aminophenoxy-acetylamino) -l-amino-benzene in 300 parts of water was acidified with 9.1 parts of hydrochloric acid and stirred to a complete solution. The solution was cooled to 0 C. by adding ice and then tetrazotized by adding 6.9 parts of sodium nitrite with good agitation. The temperature was held at 05 C. for one-half hour and a distinct test for excess nitrite was maintained to complete the tetrazotization.

A solution was made by dissolving 25.2 parts of 2-amino-5-naphthol-'T-sulfonic acid in a water solution of soda ash containing 480 parts of water and 5.7 parts of soda ash. This solution was cooled to 0 0., 31.8 parts of soda ash were dissolved in the solution and the solution of the tetrazo was slowly added whilst maintaining the temperature at 0-5 C. The mixture was then stirred one hour after all the tetrazo had been "added.

tering.

The press cake was slurried with 700 parts of water, and 13.8 parts of hydrochloric acid were added. The mixture was cooled to 5 C. and tetrazotized by adding 6.9 parts of sodium nitrite and maintaining a strong test for excess nitrite and a temperature of 5-10 C; for one hour.

A solution composed of 16.5 parts of resorcinol and 150 parts of'water was cooled to 0 C. by adding about parts of ice and 37 parts of soda ash were added.

The tetrazo slurry was slowly run into the solution of resorcinol whilst maintaining good agitation and a temperature of 0-5 G. and'then the mixture was stirred one hour after the tetrazo had all been added. The product was isolated by heating the slurry to 60-65 (7., salting slowly to 5% on the volume, filtering and drying in an oven at 75 C. The dry powder hada red-brown appearance.

The dye is represented by the formula When dyed on cotton or regenerated cellulose fibers and treated with formaldehyde as hereinafter described, the dyeing was a bordeaux shade having excellent fastness to washing and good discharge properties.

The fibers were dyed and after-treated as follows: A dyebath was made by dissolving 0.3 g. of the product in 100 cc. of water at l90-200 F., adding 0.2 g. of sodium carbonate to assist the solution. The bath was diluted with stirring to a total volume of 500 cc. with water at approximately 160 F. and 40 cc. of a solution of Glaubers salt were. added. A 10 g. piece of regenerated cellulose rayon was wet out with water, squeezed partially dry and entered into the dye bath. The temperature of the dye bath was then raised to 180-190 F. in the course of fifteen minutes and the piece was held in the bath at that temperature for one hour with stirring at frequent intervals. At the end of one hour, the dyeing was removed and rinsed in cold water.

The after-treatment may be done in s. fresh bath as follows:

The rinsed dyeing from the above operation was entered into 500 cc. of water at 130-l40 F. and 10 cc. of 10% formaldehyde cc. of approximately 37% formaldehyde by weight diluted to 250 cc. with water) were added. The

HIIT- NaOaS OH 5 NI' sNa I @OH dyeing was held in the bath at this temperature for twenty minutes and then removed, rinsed and dried.

The after-treatment may also be done in the dye bath. This is the preferred procedure because of its economy and ease of application. It is carried out as follows: At the end of the dyeing period and without removing the dyeing, 10 cc. of 10% formaldehyde are added to the dye bath and the bath is maintained at about 130140 F. for about 20 minutes. After twenty minutes or for such other time as is necessary to form a formaldehyde complex with the dye, it is rinsed and dried.

Example II By following the procedure of Example 1, except substituting 41.? parts of 2-(4'-amino-3'- sulfo-phenylamino) -5-naphthol-'7-sulfonic acid for 25.2 parts of 2-amino-5-naphthol-7-sulfonic acid, another product was made.

The dried product was dark brown in appearance. When dyed on regenerated cellulose rayon from a water bath and after tre'ated with formaldehyde as directed in Example I, the dyeing was a rubine shade possessing excellent washing fastness and good discharge properties.

The dye is represented by the formula l aNa Earample III By following the procedure of Example I and substituting for 12.9 parts of 3-(4'-aminophenoxy acetylamino)-1--amino benzene, 12.9 parts of 4-(4'-amino-phenoxy-acetylamino) -1- amino-benzene, and for 25.2 parts of 2-amino-5- naphthol-7-sulfonic acid, 37.7 parts of 243'- amino benzoyl amino) -5-naphtho1-7-sulfonic acid, another product was made.

The dry powder was red-brown in appearance.

When dyed on regenerated cellulose rayon and after-treated with'formaldehyde as directed in Example I, the dyeing was scarlet having excellent washing fastness and good discharge properties.

The dye is represented by the formula Example IV By following the procedure of Example I and substituting for 12.9 parts of 3-(4-aminophenOX acetylamino) -1-amino benzene, 20.3 parts of 1,3-di(4-a.mino-phenoxy-acetylamino)- benzene and for 25.2 parts of 2-amino-5-naphthol-7-sul1onic acid, 23.1 parts of 1-(3'-aminophenyl)-5-pyrazolone-3-carboxylic acid another dye was made.

5 The dry powder was a yellow brown in appearance. When dyed on regenerated cellulose rayon from a water bath and after-treated with formaldehyde as directed in Example I, the dyeing was an orange shade and'had excellent fastness m and good discharge properties.

The dye is represented by the formula:

40 h In the following table other modifications of the invention are set forth. The products given in the table were prepared by methods similar to those described in the preceding examples. The dyeings produced with these compounds on re- 45 generated cellulose rayon had properties similar 7 to those of the preceding examples. Arrows point from the compounds which were tetrazotized and toward the coupling components, it being understood that the couplings were made in the order stated and the shade is that of the formaldehyde 75 after-treated dyeing.

Table Example Combination shade V 4-(4-amino-phenoxy-acetylamino)-1-amino-benzene (1-(3-aminohen 1-5- razolone-3- b VI 4 zy g g y yg w jl b (I D 7) D37 car oxylic acid): Orange.

-amino-p enoxy-ace y amino -aininoenzene 2- 4 -amino-3-Sulfo hen lamino -5-na hth lacid): (I-B-dihydroxy-benzenc)z. p y p o 7 suuomc Mama VII 3-(4'ammo-phenoxy-acetylamino)-1-amino-benzene (1-(3'-amino-phenyl)-5-pyrazolone-3-carboxylic acid); Orange. VIII 3 (4' (l'a'iiilhydmxydtjeimnehj 1 b 4' 11 amine-p enoxy-ace y amino -a1ninoenzene 2- -amino-3 -su1foen lamino -5-11a hth l- 4 acid): 3 (l-3-dihydroxy-benzene)2 p Y p O 7 Home Vmlet' IX 4-(4'-am1no-phenairy-acetylamino)-l-am1no-naphtha1ene3 (1-(3-amino-phenyl)-5-pyIazolone-3-carboxy1icacid); Orange. X 4 K? (l-3-iilihydroxy-beiizene)a.1 hull v -arnmo-p epoxy-ace y amino -amino-nap a one 2- 4-amino-3 -su1fohen l-amino h Sui ionic acidh 2 (I-B-dihydroxy-benzene)z. p y 5 nap thol 7 Vwlet' XI 1,3-d1-(4f-amino-phenoxy-acetylamino)-benzene 3 (1-(3' -amino-phenyl)-5-pyrazolonc-3-carboxylic acid); Orange.

(l-ii-dihydroxy-benzene)z. XII 1,3-d i-(4-(4'-an1ino-phenoxy-acetylamino)-benzene I (2-(4-amino-3-sulio-phenylamino)-5-naphthol-7-sulfonic Rubine.

acid); :2 (l-B-dihydroxy-benzene)z. XIII 1-4-di-(4-amino-phenoxy-acetylamino)-naphthalene-6-sulionic acid I; (2-(3-amino-benzoylamino)-5-naplitho1- Red- 7-sulfonic acid); 3 (1-3-dihydroxy-benzenc)z. b XIV 1-4-(11-(4'-amino-phenoxy-acetylamino)-naphthalene-6-sulfon1c acid 2 (2-amino-5-naphthol-7-sulfonic acid); Rubine.

:3 (l-3-dihydroxy benzene. XV l-ii di-( y-amino-phenoxy-acetylamino)-benzcne-5-sulfomc acid (l-(3-amino-phenyl)-5-pyrazolone-3-carboxy- Orange.

110 acid); (1-3-dihydroxy-benzene)2. XVI 1-3-d1-(4-amino-phenoxy-acetylamino)-benzenc-5-sulfomc acid:(2-(4'-amino-3-sulfo-phenylamino)-5-naphthol- Rubine'.

7-snlfonic acid); 3 (I-S-dihydroxy-benzene)2. XVII 1-3-d1 (4'-amino-phenoxy-acetylamino)-benzcne-5-sulfonic acld (2(3-amino-benzoylamino)-5naphthol-7-sul- Scarlet.

f0lJ lB acid); 3 (I-B-dihydroxy-benzene)2. XVIII l-rz-ldg-giflgaiglno-pganew-acetylamino)-bcnzene-5-sul[onic acid (Z-amino-5-naphtl1ol-7-sulfonic acid); 1-: B rd a 1 y roxyenzene z. XIX 1-3-di-(yamino-phcnoxy-acetylamino)-benzene-5sultonic acid 3 (l-amino-5-naphthol-7-sulfonic acid); Red- (l-3-dihydroxy-benzene)z. brown. XX 4-(4-an1ino-phenoxy-acetylamino)-l-ammo-benzene 3 (2-(3-am1no-benzoy1an1in0)-5-napl1thol-7-sulfonic acid) I Scarlet.

-3-dihydroxy benzene. XXI -(gamigo-pher3oxy-acetylamino)-1-amino-beneene 3 (l-amino-5-naphthol-7-sulfonic acid): 2 (1-3-dihy- Redroxyenzene z. b XXII 4-g1-am1{)10-phcn;)Xy-a(:el;ylamll10)-l'21mlI10-beI1ZG1le 3 (2-am1no-5-naphthol-7-sulionic acid): (i-a-dihy- M3335,

roxyenzenc l. XXIILHV 3-(4-amino-phwaxy-acetylamino)-l-amino-benzcne (2-(3 -ammo-bcnzoylamino)-5-naphthol-7-sulfonic acid): Scarlet. '12; (1-3-dihydroxy-benzeneh. XXIV.--" 3-g1-amio-phen)oxy-acetylamino)-1-amino-bcnzenc (l-amln0-5-napl1thol-7-sulfonic acid); 2, (LB-dihy- R d.

roxyenzene b XXV c eg -emit]?o-phenfxy-acetylammo)-1-am1no-bcnzene 3 (Z-amm0-5-naphthol-7-sulfonic acid): 3 (l-3-dihy- 1301 331 roxyenzene 2. XX"L 4-(4':an1ino-phenoxy-acetylamino)-1-amino-naphthalene 3 (2-(3-amino-benzoy1amino)-5-naphthol-7-sulfonic Redacid) t (1-3dihydroxy-benzeneh. brown, XXVIL... 4-%gminogihenoxg acetylamino)-1-am1no-naphthalcne 3 (l-amlno-fi-naphthol-7-sultonic acid)z 2 (1-3di- Chocolate y roxyenzene 2. b XXVIII 4-(4-amino-pl1encity-acetylamino)-l-ammo-naphthalene (2-ammo-5-naphthol-7-sulfonic acid)z (1-3-di- Bio a hydroxy-benzeneh. chocolate b XXIX 1-3-di-(4'-amino-phenoxy-acetylarnino)-benzene t (2-(3-ammo-benzoy1ammo)-5-naphthol-7-sulionic acid); Sealleg? '3 (1-3- dil1ydroxy-benzene)z. XXX .i l-asdi-(4-ammo-phenoxy-acetylam1no)benzene (z-amnio-5-naphthol-7-sulfonic acldh 3 (I-B-dihydroxy- M r enzen 2. XXXI l-Iigdi-(yamino-phenoxy-acetylamino)-benzcne l-amino-5-naphthol-7-sulfonic acid): (l-3-dihydroxy- Red.

enzene 2- The treated dyeings which are made in accordance with the invention have better washing fastness than dyeings made with direct colors. The washing fastness is as good as dyeings made from diazo or developed colors and in some cases better. The initial dyeings do not change shade markedly when treated with formaldehyde as do the diazo colors upon development. Accordingly, the invention provides for dyeings having excellent washing fastness together with brightness as well as good discharge properties and other properties which are desirable and valuable in dyed fabrics. Superior dyeings are more economical to produce with the compounds of the invention than with diazo colors. This is due in part to the fact that the dyeing operations are simpler, a smaller number of operations is required and the operations are more easily controlled.

Minor variations in the processes of coupling known to those who are skilled in the art can be made. Likewise variations in the concentration, temperature and duration of the after-treating processes can be made to suit special circumstances. Any alkali-metal salts can be used instead of the sodium salts and any of the halogen derivatives can be used instead of the chloro derivatives in making the compounds.

Resorcinol is the preferred end component of this class. There are various modifications of the invention which give dyeings having an exceptionally good balance of the improved properties. Such modifications are those in which the Y components are amino naphthol sulfonic' acid and the hereinbefore indicated derivatives thereof and the amino-phenyl-pyrazolones and their derivatives; and the X components are represented by the formula As other illustrations of the many X com ponents which can be used to make products having the general properties of those hereinbefore described are r 4-'[alpha-(3'-chloro-4'-amino-phenoxy-caproyl amino) l-1-amino-2,5-dimethoxyebenzene, We claim:. ,-di.(2'-ch1oro-4'-amino-5'-methy1 p a 1. An azo compound of the group consisting aBBlIy1amin0)-beI1Zen8, of the. acids and the, alkali metalsalts, thereof -(4am n -p yyla i o)- e Y -which in the acid form are represented by the 4-amino-:naphthalene-6 -sulfonic acid, f l

0H OH H2N HMQ Y 0- :-HNAn-1-Nm Y O-OH '0 I R!!! RI]!!! diialpha -(3'1-'amin0 phe o y y ylin which Qis one of a group consisting of amino)]-naphtha1ene5-0arboxy1i0 id, branched and straight chain aliphatic hydro- 1-(4'-amino phenoxy acetylamino) -4-aminocarbon radicals having 1 to 6 carbons; each R 5-methoxy-naphthalene-7-sulfonic acid, is from the group consisting of hydrogen, alkyl 2-(3'- amino phenoxy acety1amin0)- -a n having 1 to 6 carbons, the corresponding alkoxy naphthalene fi-sulfonicacid. groups, carboxy, sulfonicv acid and halogen; 1-(4'- amino-Dhenoxy-acetyla o) 4 R""' is one of a group consisting of hydrogen, Chlo n p t alenB-fi-carboxylic acid, alkyl having 1 to 6 carbons, the corresponding l-ta'amino-fi'-methy1-phenoxy-acetylamin0)- alkoxy groups, hydroxy, sulfonicaoid and caramino-benzene-5-carboxylic acid, boxy; -HN-ArylNHz is one of a group con- 1-[a1pha-(4- amino phenoxy-acety1amino)l-4- sisting of radicals of the benzene and naphthaamino2,5-dich1oro-benzene, and lene series represented by the formulae 1-(2- amino phenoxy acetylamino) -3-:amino- Z benzene. I As illustrations of'other variations of the Y components are mentioned aniline, l-amino-2- (R)n methoxy-5emethyl-benzene, 1-amino-3- methy1- and R benzene, 1-amino-naphthalene-6-sulfonic acid, z 2-amino-8-naphthol-6-sulfonic acid, 2-amino-8- naphthol-3,6-disulfonic acid, 1-(4'-amino-3'- sulfo phenylamino) 5 naphthol 7 sulfonic acid, 1 (3 amino benzoylamino) 5 naphthol-T-sulfonic acid, 1-amino-2-methoxy-naphthaleneefi-sulfonic acid, l-amino-B-chloro-naphthalene-fi-sulfonic acid, l-amino-naphthalene- 6- carboxylic acid, 2 amino 3 methyl 5 naphthol-7-sulfonic acid, 2-(4-amino-3-methyl 5 sulfo phenylamino) 5 naphthol 7 sulfonic acid, 2 (3' amino 5 sulfo phenylamino) 5 naphthol '7 sulfonic acid, 2 (3' amino 4" ethoxy benzylamino) 5 I I NH? naphthol 7 sulfonic acid, 2 (3 ammo 4 E i wherein R is from the group consisting of hydrogen, halogen, carboxy and sulfonic acid; R" is from the group consisting of hydrogen, halogen, alkyl having 1 to 6 carbons and the corresponding alkoxy groups; n is 1 to 2; m is 1 to 2; and Z is one of a group consisting of amino and the radical propoxy 5 chloro benzoylamino) 5 naphthol 7 sulfonic acid, 1 (3' amino 5' carboxy-phenyl) 5 pyrazolone 3 carboxylic acid, 1 (3' amino 5' sulfo phenyl) 5 pyrazolone-B-carboxylic acid, 1-(3'-amino-4- NH chloro 5' ethyl phenyl) 5 pyrazolone 3 i carboxylic acid, 1-(3' -arnino-5'-bromo-benzoylamino) -5-naphthol-7-sulfonic acid, 1-(4'-amino 3'- carboxy phenyl) 3 methyl 5 pyrazolone, 2 (4" methoxy 3' amino-benzoylamino) 5 naphthol 7 sulfonic acid, 2 (4' amino benzoylamino) 5 naphthol 7 sulfonic acid, and 2- [4-methoxy-3'- (4"-aminobenzoylamino) benzoylamino] 5 naphthol 7-sulfonic acid..

As illustrations of other variations of the end components are mentioned:

(Rh and each Yis one of a group represented by the following formulae H NH:

H 5-methyl- 1,3 -diliydroxy-benzene, I f NH 3,5-dihydroxy-benzene-l-carboxylic acid, 3,5-dihydroxy-benzene-1-sulfonic acid,

1,3 ,S-tri-hydroxy-benzene, 55 1-methoxy-3 .5 -dihydroxy-benzene,

1-propoxy-3,5-dihydroxy benzene, and 1-hexyl-3,5 dihydroxy benzene.

N From the foregoing disclosure it will be recog- I NH niz'ed that the invention is susceptible of modification without departing from the spirit and (R').. scope thereof and it is to be understood that the invention is not restricted to the specific illus- H trations thereof herein set forth. D R

wherein -H represents the coupling position; one D is hydroxy and the other is hydrogen; the M which is meta to hydroxy is sulfonic acid and the other M is hydrogen; R is from the group consisting of hydrogen, carboxy, and sulfonic acid; R"" is one of a group consisting of methyl and carboxy; and R"" is one of a, group consisting of hydrogen, alkyl and alkoxy; said compound containing at least one solubilizing group.

2. An azo compound of the group consisting of the acids and the alkali metal salts thereof which in their acid form are represented by the formula Kj RIHIII) n wherein HNAry1-NH2 is one of a group consisting of radicals of the benzene and naphthalene series represented by the formulae in which each R. is one of a group consisting of hydrogen, lower alkyl and alkoxy, carboxy, sulfonic acid and halogen; R is from the group consisting of hydrogen, halogen, carboxy and sulfonic acid; R" is from the group consisting of hydrogen, halogen, lower alkyl and the corresponding alkoxy groups; n is 1 to 2; m is 1 to 2; and Z is one of a group consisting of amino and the radical one D is hydroxy and the other is hydrogen; the M which is meta to hydroxy is sulfonic acid and the other M is hydrogen; R is from the group consisting of vhydrogen, carboxy, and sulfonic acid; R" is one of a group consisting of methyl and carboxy; and R""" is one of a group consisting of hydrogen, alkyl and alkoxy; said compound containing at least one solubilizing group.

3. An azo compound of the group consisting of the acids and the alkali metal salts thereof which in their acid form are represented by the 8. The formaldehyde complex of a compound formula of claim 2.

HaNOOOHpF-HN- l A I NH:

t D M D M I I I I I Q I NH: l NH: ")n i (R)m i OH OH H OH wherein R" is from a group consisting of hydro- 9. The formaldehyde complex of a compound gen, halogen, alkyl having 1 to 6 carbons, the corof claim 3. responding alkoxy groups and halogen; m is 1 to 10. The formaldehyde complex of a compound 2; one D is hydroxy and the other is hydrogen; of claim 4. the M which is meta to hydroxy is sulfonic acid 25 11. The formaldehyde complex of a compound and the other is hydrogen. of claim 5. V

The compound represented by the formula 12. The formaldehyde complex of a compound 1 of claim 6.

lfil-O-O-Cl-Ir-fi-HNQ 13. The formaldehyde and metal complex of a N SOINa Q N 30 compound of claim 1.

I I H 14. Th formaldehyde and metal complex of f a compound of claim 2.

OH HO 15. The formaldehyde and metal complex of a compound of claim 4.

N=N H 35 16. The formaldehyde and metal complex'of a compound of claim 5. N-N- H O 17. The formaldehyde and metal complex of 5. The compound represented by the formula a compound of claim 6.

6. The compound represented by the formula on, on

. NaO S r -01; i I oH OH 7i The formaldehyde complex of a compound CHILES- E. SPARKS.

of claim 1. V JAMES W. LIBBY, JR, 

